Azo dye and method for its preparation



Patented Get. 9, 1934 UNETED STATES PA'EEENTTQFFICE AZO DYE AND METHOD FOR ITS PREPARATEON Miles Augnstinus Dahlen, Wilmington, Del., as-

signor to E. l. du Pont de Nemonrs & Company, Wilmington, Bet, a corporation of Delaware No Drawing. Application June 30, 1932,

Serial No. 620,285

12 Claims. (Cl. 260-76) This invention relates to new azo dyestufis benzene, or carbazole, which contains no group, which are insoluble in water and yield valuable such as the sulfonic acid or carboxylic acid pigment dyes or fast dyeings and printings when group, which would render the dyestuff water prepared on the fiber. soluble, but which may contain groups such as It is an object of this invention to prepare alkyl, alkoxy, halogen, nitro, and benzoylamino; 6o azo dyes which exhibit good fastness to washing, and A has the same meaning as in the preceding light and chlorine. Another object is to prepare paragraph. azo dyes which impart beautiful bright colors In order to more completely understand the to the material dyed and which may be produced present invention reference may be had to the either as insoluble pigments in aqueous solution following examples in which the quantities are 65 or suspension, or on the fiber. Additional obstated in parts by weight: I jects will appear hereinafter. I V 7 These objects are attained by the process of Example 1 the present invention wherein an arylamide of beta-hydroxy-naphthoic d av t Cotton yarn, after being well boiled anddried, 70

lowing general formula: was impregnated thoroughly with an aqueous padding liquor containing in one liter 10 parts of the cli-(2 3-hydroxy-naphthoyl)-derivative of the di-(para-amino-phenyl) -ether of ethylene-glycol, parts of caustic soda of -oo HAOCH on OA o 7 N 2 2 NH O strength, and 40 parts of Turkey red oil of 50% strength. The yarn was then wrung out and dein which A represents a benzene nucleus which veloped without drying in a diazo solution premay have groups substituted thereon such as pared as follows:

25 halogen, alkyl, alkoxy, and nitro, is coupled with 16.5 parts of 2-5-dichloroaniline were boiled a diazotized aromatic amine which is free from w 0 parts of Water Containing 50 Parts Of any group rendering the dyestuff water soluble; hydrochloric acid of 20 B. The solution was The dyes produced thereby have the following COOlQd, 200 parts of ice were added, and then general formula; S'parts" of sodium nitrite of 95% strength dis- I 7 3O solved in,30 parts of water were gradually added.

Aryl Aryl When diazotization was complete, the solution l; t was filtered. The solution was then treated with I! ll enough sodium acetate to neutralize the mineral acidity. 35 OH HO After the development of the dyestuff in the above bath was completed, the yarn was rinsed and then soaped in boiling water. Upon further rinsing and drying, a bright scarlet dyestuif r Was obtained possessing very good fastness to 40 in which Aryl represents benzene, diphenyl, di-Z chlorine; boiling water and light. Following is phenylamine, naphthalene, anthraquinone, azothe probable formula of the dyestuff:

OH H0 55 I GONHG -OEGEt-OONHCO Example 2 a diazo solution prepared as follows:

17 parts of 4-chloro-2-nitro-aniline were dissolved at -90 C. in 30 parts of sulfuric acid The solution was then poured into cold water and ice with stirring and diazotized at a low temperature with a solution of sodium nitrite,

Before use, the diazo solution was made neutral to Congo red paper by the in the usual manner.

addition of sodium acetate.

When the development of the dyestufl was complete, the yarn was rinsed, boiled with a soap solution, rinsed further and dried. The dyestufi produced was a brilliant scarlet, fast to light and washing. The probable formula of the color is given below:

if N

CON

As will be readily understood, the number of dyestuffs prepared according to the present in- The following table cites a few representative examples and includes a devention is very large.

| HQ O-NHO 1 31 NHOO OuH;

' OCH:

OH O

on nooorvrrOoomomoGmroo Similarly, No. 21 has the probable constitution:

scription of the shades produced on cotton materials.

Combined with the di-(2z3-hy- Exdroxy naph- Developed with the ampl thoyl) deriva Shade No. tive of the following diether of ethylene glycol 3 Meta-chloro-aniline 4 chloro 2 am Orange.

ino-phenyl. 4 l-omino-4-benzoyld0 Blue.

amino 2,5 dimeth oxy-benzene. 5 4 nitro 2 amino do Reddish scaranisole. let. 6 2,5-dichloro-aniline 2 methoxy 4 Scarlet.

amino-phony]. 7 5 nitro 2 amino Bluish-red.

anisole. 8 3-amin0-earbazole-.- do Bluish-black. 9 1 amino 4 benzoyl Ortho amino Blue.

amino -2,5 dimeth phenyl. 0xy-bcnzene. l0 Meta-chlor0an1lme do Orange. 11 4 nitro 2 amino do Reddish-scaranisole. let. 12 2,5-dichloroaniline.. do Yellowish-scaret. 13 5 nitro 2 amino do Bluish-rcd.

anisole. 14 Meta-chloro-aniline Para amino Orange.

phenyl. l5 5 nitro 2 amino do Bluish-red.

anisole. 16 Ortho phenetole do Blue-black.

azo alpha naph thylamine. 17 2 nitro 4 methyl d0 Corinth.

benzene azo eres idine. 18 3 nitro 4 amino do Scarlet.

toluene. 19 l-amino-4-benzoy1- do Deep blue. amino -2,5 dimethoxy-benzene. 20 Alpha-naphthylamine do Maroon. 21 Alpha-amino-anthrad0 Red.

quinone. 22 Ortho-dianisidine do Blue. 23 4,4 diamino diphe do Blue-black.

nylarnine.

All of the above dyestuffs show good to excellent 11.5. fastness to light, chlorine and hot soaping. Those prepared from the di-para-amino-phenyl ether show in general the best fastness to light.

The probable formulas of the respective dyestuffs follow from their mode of preparation. For example No. 19, probably possess the constitution:

NHCOCQHI OCH:

N II N l II N OH HO- GONE-QOCHzOHzO-G-NHCO In practicing the present invention the aromatic amine may have various groups substituted. thereon provided that these groups donot render the resulting dye water soluble. Also, as above mentioned, the nucleus represented by A'may have groups substituted thereonsuch as halogen, alkyl, alkoxy, and nitro. I

The arylamides of beta-hydroXy-naphthoic acid may be prepared by any of the well known methods, some of which are described in copending application No. 438,913, filed March 25, 1930.

The products of the present invention are characterized by a satisfactory fastness to washin light and chlorine. In addition, they impart'brilliant colors to the dyed material.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is'to be understood that I do not limit myself to the specific embodiments thereof except as defined in the appended claims.

I claim:

1. A process for preparing water insoluble azo dyes which comprises coupling an arylamide of beta-hydroXy-naphthoic acid of the following general formula:

OH HO- in which A represents a benzene nucleus, with a diazotized aromatic amine.

2. A process for preparing water in soluble azo dyes which comprises coupling an arylamide of beta-hydroxy-naphthoic acid of the following general formula:

OH HO- in which A represents a benzene nucleus, which may have substituted thereon members selected from the group consisting of halogen, alkyl, alkoxy, and nitro, with a diazotized aromatic amine selected from the group consisting of benzene, diphenyl, diphenylamine, naphthalene, anthraquinone, azobenzene and carbazole, which may have substituted thereon members selected from the group consisting of alkyl, alkoxy, halogen, nitro, and benzoyl-amino.

3. A process for preparing water insoluble azo dyes which comprises coupling an arylamide of beta-hydroxy-naphthoic acid of the following 4 general formula:

OH HO- OONH-A-OCHzCHzO-A-NHCO in which A represents a benzene nucleus, which may have substituted thereon members selected from the group consisting of halogen, alkyl, alkoxy, and nitro, with a diazotized aromatic amine of the benzene series which may have substituted 0 ONH-O-O-CHzCHrOONH on no in which Aryl represents an aromatic nucleus, and A represents a benzene nucleus.

7. A water insoluble azo dye having the following general formula:

illryl ilkryl OH HO in which Aryl represents an aryl nucleus selected from the group consisting of benzene, diphenyl, diphenylamine, naphthalene, anthraquinone, azobenzene and carbazole, which may have substituted thereon members selected from the group consisting of alkyl, alkoxy, halogen, nitro, and benzoyl-amino, and A represents a benzene nucleus which may have substituted thereon members selected from the group consisting of halogen, alkyl, alkoxy, and nitro. 1,24)

8. A water insoluble azo dye having the following general formula:

Aryl

OH HO- 0 ONH-A-OOHz'OHgO-A-NHCO- in which Aryl represents an aryl nucleus of the benzene series which may have substituted thereon members selected from the group consisting of alkyl, alkoxy, halogen, nitro, and benzoylamino, and A represents a benzene nucleus which may have substituted thereon members selected from the group consisting of halogen, alkyl, alkoxy, and nitro.

9. An azo dye having the following formula:

0 oit'll which dyes cotton yarn with a'bright scarlet color. 10. An azo dye having the following'formula:

which dyes cotton yarn with a bright scarlet color.

11. A water insoluble azo dye containing the grouping:

OH H0 CONHAOCH&OH;OANHC o in which A represents a benzene nucleus.

12. An azo dye containing the grouping:

OH HO CONH AOCHzGHZOANHCO in which A represents a benzene nucleus which may have substituted thereon radicals selected from the group consisting of halogen, alkyl, alkoxy, and nitro.

MILES AUGUSTINUS DAHLEN. 9a 

